JPWO2010098236A1 - Metal-coated polyimide resin substrate with excellent heat aging characteristics - Google Patents
Metal-coated polyimide resin substrate with excellent heat aging characteristics Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Abstract
ポリイミド樹脂フィルムの片面又は両面に、乾式法による表面改質を行った後、乾式法によりバリアー層を形成し、その後湿式法又は乾式法によりシード層を形成し、その表層に湿式法で導電性皮膜を形成した金属被覆ポリイミド樹脂基板であって、該金属被覆ポリイミド樹脂基板を90°ピール試験した後の導電性皮膜層側の剥離面において、飛行時間型二次イオン質量分析装置(TOF−SIMS)を用いた深さ方向分析によるポリイミド残渣とバリアー金属層残渣の混在層厚みがSiスパッタ速度換算で0.70nm以下であって、150°C、168時間エージング試験後のピール強度保持率(150°C、168時間エージング後ピール強度/初期ピール強度)が50%以上であることを特徴とする金属被覆ポリイミド樹脂基板を提供する。After surface modification by a dry method on one or both sides of a polyimide resin film, a barrier layer is formed by a dry method, and then a seed layer is formed by a wet method or a dry method, and the surface layer is conductive by a wet method. A metal-coated polyimide resin substrate having a film formed thereon, and a time-of-flight secondary ion mass spectrometer (TOF-SIMS) on a peeling surface on the conductive film layer side after the 90 ° peel test of the metal-coated polyimide resin substrate ), The mixed layer thickness of the polyimide residue and the barrier metal layer residue is 0.70 nm or less in terms of Si sputtering rate, and the peel strength retention rate after the aging test at 150 ° C. and 168 hours (150 A metal-coated polyimide resin substrate having a peel strength after initializing at 168 ° C / initial peel strength) of 50% or more is provided. To.
Description
フレキシブルプリント基板、TAB、COF等の電子部品の実装素材として用いられる無接着剤フレキシブルラミネート材、特に耐熱エージング特性に優れた金属被覆ポリイミド樹脂基板の製造方法に関する。 The present invention relates to a method for producing a non-adhesive flexible laminate material used as a mounting material for electronic components such as flexible printed circuit boards, TAB, and COF, particularly a metal-coated polyimide resin substrate having excellent heat aging characteristics.
ポリイミドフィルムに主として銅からなる金属導体層を積層したFCCL(Flexible Copper Clad Laminate)は、電子産業における回路基板の素材として広く用いられている。中でも、ポリイミドフィルムと金属層との間に接着剤層を有しない無接着剤フレキシブルラミネート(特に、二層フレキシブル積層体)は回路配線幅のファインピッチ化に伴い注目されている。 FCCL (Flexible Copper Clad Laminate) in which a metal conductor layer mainly made of copper is laminated on a polyimide film is widely used as a material for circuit boards in the electronics industry. Among these, non-adhesive flexible laminates (especially two-layer flexible laminates) that do not have an adhesive layer between a polyimide film and a metal layer have attracted attention as the circuit wiring width becomes finer.
無接着剤フレキシブルラミネート、特にファインピッチに対応した無接着剤フレキシブルラミネートの製造方法としては、ポリイミド樹脂フィルム上にスパッタリング、CVD、蒸着などの乾式めっき法によりバリアー層及びシード層を予め形成し、次いで電解めっき法により導体層となる金属層を成膜する、いわゆるメタライジング法がある。
このメタライジング法においては、金属層とポリイミドフィルムとの密着力を高めるために、金属層を形成するに先立ち、ポリイミド樹脂フィルム表面をプラズマ処理することにより、バリアー金属との密着性向上を目的とした表面改質を行うことが行われている(特許文献1及び特許文献2参照)。As a method for producing an adhesive-free flexible laminate, particularly an adhesive-free flexible laminate corresponding to fine pitch, a barrier layer and a seed layer are previously formed on a polyimide resin film by a dry plating method such as sputtering, CVD, and vapor deposition. There is a so-called metalizing method in which a metal layer to be a conductor layer is formed by an electrolytic plating method.
In this metallizing method, in order to increase the adhesion between the metal layer and the polyimide film, the polyimide resin film surface is subjected to plasma treatment prior to the formation of the metal layer for the purpose of improving the adhesion with the barrier metal. Surface modification has been performed (see
また、ポリイミド樹脂フィルムに無電解めっきによりバリアー層およびシード層を予め形成し、次いで電解めっき法により導体層となる金属層を成膜するものも提案されている。
この方法においては、金属層を形成するに先立ち、ポリイミド樹脂フィルムをアルカリ金属水酸化物からなる溶液に浸漬し、後の無電解めっきの駆動力となる触媒の吸着向上およびバリアー金属との密着性向上を目的とした表面改質が行われている(特許文献3参照)。In addition, it has also been proposed that a barrier layer and a seed layer are previously formed on a polyimide resin film by electroless plating, and then a metal layer to be a conductor layer is formed by electrolytic plating.
In this method, prior to the formation of the metal layer, the polyimide resin film is immersed in a solution made of an alkali metal hydroxide to improve the adsorption of the catalyst, which becomes the driving force for the subsequent electroless plating, and the adhesion to the barrier metal. Surface modification for the purpose of improvement is performed (see Patent Document 3).
前記ポリイミド樹脂フィルムの表面改質処理は、ポリイミド樹脂フィルムと金属層との密着性に大きな影響を及ぼしており、製造上に特に重要な処理工程になっている。 The surface modification treatment of the polyimide resin film has a great influence on the adhesion between the polyimide resin film and the metal layer, and is a particularly important treatment step in production.
無接着剤フレキシブルラミネートに求められる機械的特性としては、初期のピール強度と長期経過後におけるピール強度が重要なものであり、近年では高信頼性要求として特に長期経過後のピール強度が重要となってきている。
また、長期経過後のピール強度の評価方法としては、一般に加速劣化試験である耐熱エージング(150°C、168時間)後のピール測定によって評価されている。As the mechanical properties required for adhesive-free flexible laminates, the initial peel strength and the peel strength after a long period of time are important. In recent years, the peel strength after a long period of time has become particularly important as a requirement for high reliability. It is coming.
Moreover, as a method for evaluating peel strength after a long period of time, it is generally evaluated by peel measurement after heat aging (150 ° C., 168 hours), which is an accelerated deterioration test.
最近では、改質処理されたポリイミド樹脂フィルムを硝酸銀水溶液によって染色して透過電子顕微鏡(TEM)で断面を観察し、その改質層の厚さにより、初期および耐熱エージング後のピール強度を決定する方法が提案されている(特許文献4参照)。
しかしながら実際のポリイミド樹脂フィルムの表面改質においては、処理条件によって密着性に寄与する官能基を含む様々な分子構造を持つものが生成するため、上記の方法では、硝酸銀に染色される表面改質層を特定の物質のみで評価しているに過ぎず、上記評価での改質層厚さが同様であっても、実際のピール強度試験結果との間に差異が生じるといった問題があった。Recently, the modified polyimide resin film is dyed with an aqueous silver nitrate solution, the cross section is observed with a transmission electron microscope (TEM), and the peel strength after initial and after heat aging is determined by the thickness of the modified layer. A method has been proposed (see Patent Document 4).
However, in the actual surface modification of the polyimide resin film, those having various molecular structures including functional groups that contribute to adhesion are generated depending on the processing conditions. The layer was evaluated only with a specific substance, and there was a problem that even if the modified layer thickness in the above evaluation was the same, there was a difference between the actual peel strength test results.
本願発明は、金属被覆ポリイミド樹脂フィルムと金属層との初期密着力を低下することなく150°C、168時間エージング後の密着力が高い金属被覆ポリイミド樹脂基板を提供することを目的とする。 An object of the present invention is to provide a metal-coated polyimide resin substrate having high adhesion after aging for 150 ° C. and 168 hours without reducing the initial adhesion between the metal-coated polyimide resin film and the metal layer.
上記の課題に鑑み、本発明は以下の発明を提供するものである。
1)ポリイミド樹脂フィルムの片面又は両面に、乾式法による表面改質を行った後、乾式法によりバリアー層を形成し、その後湿式法又は乾式法によりシード層を形成し、その表層に湿式法で導電性皮膜を形成した金属被覆ポリイミド樹脂基板であって、該金属被覆ポリイミド樹脂基板を90°ピール試験した後の導電性皮膜層側の剥離面において、飛行時間型二次イオン質量分析装置(TOF−SIMS)を用いた深さ方向分析によるポリイミド残渣とバリアー金属層残渣の混在層厚みがSiスパッタ速度換算で0.70nm以下であり、150°C、168時間エージング試験後のピール強度保持率(150°C、168時間エージング後ピール強度/初期ピール強度)が50%以上であることを特徴とする金属被覆ポリイミド樹脂基板。In view of the above problems, the present invention provides the following inventions.
1) After surface modification by a dry method on one or both sides of a polyimide resin film, a barrier layer is formed by a dry method, and then a seed layer is formed by a wet method or a dry method, and the surface layer is formed by a wet method. A time-of-flight secondary ion mass spectrometer (TOF) on a peeled surface of a metal-coated polyimide resin substrate on which a conductive film is formed and the metal-coated polyimide resin substrate is subjected to a 90 ° peel test on the conductive film layer side. -SIMS), the mixed layer thickness of the polyimide residue and the barrier metal layer residue by the depth direction analysis is 0.70 nm or less in terms of Si sputtering rate, and the peel strength retention after the aging test at 150 ° C for 168 hours ( A metal-coated polyimide resin substrate having a peel strength after aging for 150 ° C. for 168 hours / initial peel strength) of 50% or more.
また、本願発明は、次の発明を提供する。
2)前記シード層及び導電性皮膜が銅であり、前記バリアー層は、ニッケル、クロム又はこれらの合金であることを特徴とする上記1)記載の金属被覆ポリイミド樹脂基板。
3)前記ポリイミド樹脂フィルムにおける乾式法の表面改質は、プラズマ処理により行うことを特徴とする上記1)又は2)記載の金属被覆ポリイミド樹脂基板。The present invention provides the following invention.
2) The metal-coated polyimide resin substrate according to 1) above, wherein the seed layer and the conductive film are copper, and the barrier layer is nickel, chromium, or an alloy thereof.
3) The metal-coated polyimide resin substrate as described in 1) or 2) above, wherein surface modification of the polyimide resin film by a dry method is performed by plasma treatment.
本願発明は、ポリイミド樹脂フィルムの片面又は両面に、乾式法による表面改質を行った後、乾式法によりバリアー層を形成し、その後湿式法又は乾式法によりシード層を形成し、その表層に湿式法で導電性皮膜を形成した金属被覆ポリイミド樹脂基板であり、特にポリイミドフィルムと金属層間の積層後の初期密着力を低下させることなく、エージング後の密着力を高めることができるという優れた効果を有する。 In the present invention, after surface modification by a dry method is performed on one or both sides of a polyimide resin film, a barrier layer is formed by a dry method, and then a seed layer is formed by a wet method or a dry method, and the surface layer is wet. This is a metal-coated polyimide resin substrate on which a conductive film is formed by the method. Especially, it has the excellent effect that the adhesion after aging can be enhanced without reducing the initial adhesion after lamination between the polyimide film and the metal layer. Have.
一般に、ポリイミド樹脂フィルムの片面又は両面に湿式法又は乾式法による表面改質を行った後、バリアー層を形成し、このバリアー層上にシード層を形成し、さらにこのシード層上に一定の厚みの導電性皮膜を形成して金属被覆ポリイミド樹脂基板が製造されている。本願発明において、ポリイミド樹脂フィルム上にバリアー層を形成するには、スパッタリング、CVD、蒸着などの乾式法で行うことができる。
このようにして製造されたポリイミドフィルムと金属層との間に接着剤層を有しない無接着剤フレキシブルラミネート(特に、二層フレキシブル積層体)は、FCCL(Flexible Copper Clad Laminate)として電子産業における回路基板の素材として広く用いられるが、最近の回路配線幅のファインピッチ化に伴い金属層とポリイミドフィルムとの密着力を高めることが要求されている。In general, after surface modification by a wet method or a dry method on one or both sides of a polyimide resin film, a barrier layer is formed, a seed layer is formed on the barrier layer, and a constant thickness is formed on the seed layer. A metal-coated polyimide resin substrate is manufactured by forming a conductive film. In this invention, in order to form a barrier layer on a polyimide resin film, it can carry out by dry methods, such as sputtering, CVD, vapor deposition.
Non-adhesive flexible laminates (especially two-layer flexible laminates) that do not have an adhesive layer between the polyimide film and the metal layer produced in this way are circuits in the electronics industry as FCCL (Flexible Copper Clad Laminate). Although widely used as a substrate material, it is required to increase the adhesion between the metal layer and the polyimide film with the recent finer pitch of circuit wiring width.
その評価方法として、一般に常態ピール強度(初期ピール強度)及び加速劣化試験である耐熱ピール強度(150°C、168時間エージング後のピール強度)を測定することが行われている。
上記の通り、高信頼性要求として、特に長期経過後のピール強度が重要となってきているので、150°C、168時間エージング試験後のピール強度保持率(耐熱ピール強度/常態ピール強度)を極力高めることが要求されている。As its evaluation method, it is generally performed to measure normal peel strength (initial peel strength) and heat-resistant peel strength (150 ° C, peel strength after 168 hours aging), which is an accelerated deterioration test.
As described above, since the peel strength after a long period of time has become particularly important as a requirement for high reliability, the peel strength retention rate (heat-resistant peel strength / normal peel strength) after an aging test at 150 ° C. and 168 hours is obtained. It is required to increase as much as possible.
このようなピール強度保持率を高めるためには、ポリイミド樹脂フィルムの表面に湿式法又は乾式法による表面改質処理を行うことが好ましいことが知られているが、これがどのような機構又は現象によりピール強度が増加するのか、十分に理解されておらず、また改質処理自体も試行錯誤的に実施している程度で、一定の改質レベルを保持することが難しいという問題があった。 In order to increase the peel strength retention rate, it is known that the surface of the polyimide resin film is preferably subjected to a surface modification treatment by a wet method or a dry method, but this is due to any mechanism or phenomenon. Whether the peel strength increases is not fully understood, and there is a problem that it is difficult to maintain a certain reforming level to the extent that the reforming process itself is carried out by trial and error.
このようなことから、本願発明者は、金属被覆ポリイミド樹脂基板の90°ピールにおける金属層側剥離面における深さ方向の構造を詳細に調査した。この結果、表面改質処理後に形成したバリアー層(ニッケル、クロム、これらの合金層)とポリイミドとの混在する層が存在することが分かった。
ポリイミド樹脂の改質処理方法にもよるが、一般的には改質処理が過剰であるとバリアー層金属のポリイミド改質層への混入が多くなり、バリアー層金属とポリイミドとの混在する層が厚くなる。また、バリアー層の形成におけるスパッタエネルギーが増加するに従い、ポリイミド層へのバリアー金属の打ち込みが多くなり、バリアー層金属とポリイミドとの混在する層が厚くなる。
そして、耐熱エージング後のピール強度低下が、初期のピール剥離面における金属層側のポリイミドとバリアー金属層との混在層の厚さに起因することが分かった。つまり、ポリイミドとバリアー層金属との混在層が厚いほど、この混在層を通じて触媒酸化作用を有する銅がポリイミド層へ拡散し易くなるため、ポリイミド樹脂の分子構造の劣化が促進され、耐熱エージングでのピール強度が低下することを見出した。
したがって、初期のピールにおける金属層側剥離面のポリイミドと金属混在層の厚さを調節することにより、耐熱エージング後のピール強度を高く維持することが可能であるとともに、初期の金属層側剥離面のポリイミドと金属混在層の厚さから、耐熱エージング後のピール強度を予測することが可能となることが分かった。For this reason, the inventor of the present application investigated in detail the structure in the depth direction on the metal layer side peeling surface at 90 ° peel of the metal-coated polyimide resin substrate. As a result, it was found that there was a layer in which a barrier layer (nickel, chromium, or an alloy layer thereof) formed after the surface modification treatment and polyimide were mixed.
Although depending on the modification method of the polyimide resin, generally, if the modification process is excessive, the barrier layer metal is mixed into the polyimide modified layer, and there is a layer in which the barrier layer metal and the polyimide are mixed. Become thicker. Further, as the sputtering energy in the formation of the barrier layer increases, the barrier metal is more heavily implanted into the polyimide layer, and the layer in which the barrier layer metal and polyimide are mixed becomes thicker.
And it turned out that the peel strength fall after heat-resistant aging originates in the thickness of the mixed layer of the polyimide by the side of a metal layer and a barrier metal layer in an initial peel peeling surface. In other words, the thicker the mixed layer of polyimide and barrier layer metal, the more easily the copper having catalytic oxidation action diffuses into the polyimide layer through this mixed layer, so the deterioration of the molecular structure of the polyimide resin is promoted and the heat aging It has been found that the peel strength decreases.
Therefore, by adjusting the thickness of the polyimide and metal mixed layer on the metal layer side peeling surface in the initial peel, it is possible to maintain high peel strength after heat aging, and the initial metal layer side peeling surface. It was found that the peel strength after heat aging can be predicted from the thickness of the polyimide and metal mixed layer.
図1に、金属層側のピール剥離面について、飛行時間型二次イオン質量分析装置(TOF−SIMS)の深さ方向分析を用いた、ポリイミド残渣(C−C)とバリアー金属(Ni)層残渣の混在層厚みを調査した場合の概要を示す。
図1に示すように、ポリイミド残渣(C−C)は、スパッタSi換算深さ2nm近傍でピークになり、一方バリアー金属(Ni)はスパッタSi換算深さ4.5nm近傍でピークとなっている。この中間がポリイミドと金属の混在層である。
後述する実施例及び比較例から明らかなように、この混在層の厚みの増大が耐熱エージング後のピール強度保持率の低下する原因となることが分かった。FIG. 1 shows a polyimide residue (C-C) and a barrier metal (Ni) layer using a depth direction analysis of a time-of-flight secondary ion mass spectrometer (TOF-SIMS) for the peel-off surface on the metal layer side. The outline when the mixed layer thickness of the residue is investigated is shown.
As shown in FIG. 1, the polyimide residue (C-C) has a peak at a sputtered Si equivalent depth of 2 nm, while the barrier metal (Ni) has a peak at a sputtered Si equivalent depth of 4.5 nm. . The middle is a mixed layer of polyimide and metal.
As is apparent from Examples and Comparative Examples described later, it has been found that the increase in the thickness of the mixed layer causes a decrease in the peel strength retention after heat aging.
以上から、本願発明者らは、多くの研究により、金属層側剥離面におけるポリイミドとバリアー層金属との混在層厚みが、TOF−SIMSの深さ方向分析によるSiスパッタ速度換算で0.70nm以下である場合に、150°C、168時間エージング試験後のピール強度保持率(耐熱ピール強度/常態ピール強度)が増加することが分かった。そして、この場合に、ピール強度保持率50%以上を達成することが可能となった。 From the above, the inventors of the present invention have found that the mixed layer thickness of polyimide and barrier layer metal on the metal layer side peeled surface is 0.70 nm or less in terms of Si sputtering rate by TOF-SIMS depth direction analysis. It was found that the peel strength retention (heat-resistant peel strength / normal peel strength) after an aging test at 150 ° C. for 168 hours was increased. In this case, a peel strength retention of 50% or more can be achieved.
次に、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例のみに制限されるものではない。すなわち、本発明に含まれる他の態様または変形を包含するものである。 Next, description will be made based on examples and comparative examples. In addition, a present Example is an example to the last, and is not restrict | limited only to this example. That is, other aspects or modifications included in the present invention are included.
(実施例1)
ポリイミド樹脂フィルムとして、デュポン社:カプトン150ENを用いた。このポリイミド樹脂フィルムにプラズマ処理を行い、スパッタリングによりニッケルクロム合金からなるバリアー層を25.0nmの厚みに形成した。
次に、スパッタリングによりシード銅層を形成した。続いて、電気めっきにて8μmの銅導体層を形成し、ピール強度測定を行った結果、常態ピール強度0.66kN/m、耐熱ピール強度0.36kN/mのピール特性を持つサンプルを得た。
このように形成された金属被覆ポリイミド樹脂基板について、常態ピールにおける金属層側剥離面のポリイミドとシード層金属との混在層の厚さを飛行時間型二次イオン質量分析装置(TOF−SIMS)の深さ方向分析を用い測定を行った。
図2は、バリアー金属とPI(ポリイミド)混在層の厚さ(Si換算厚さnm)に対するピール強度保持率(%)との関係を示す図であるが、この図2に示すように、バリアー金属(Ni)とポリイミド混在層の厚みがSi換算で0.53nmであり、このときのピール強度保持率(耐熱ピール強度/常態ピール強度)は55%と良好な結果であった。
上記測定の結果を、表1に示す。Example 1
As a polyimide resin film, DuPont: Kapton 150EN was used. This polyimide resin film was subjected to plasma treatment, and a barrier layer made of a nickel chromium alloy was formed to a thickness of 25.0 nm by sputtering.
Next, a seed copper layer was formed by sputtering. Subsequently, an 8 μm copper conductor layer was formed by electroplating and the peel strength was measured. As a result, a sample having peel properties of a normal peel strength of 0.66 kN / m and a heat-resistant peel strength of 0.36 kN / m was obtained. .
For the metal-coated polyimide resin substrate formed in this way, the thickness of the mixed layer of the polyimide and the seed layer metal on the metal layer-side release surface in the normal peel is measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Measurements were made using depth direction analysis.
FIG. 2 is a diagram showing the relationship between the barrier metal and the peel strength retention rate (%) with respect to the thickness of the PI (polyimide) mixed layer (Si equivalent thickness nm). As shown in FIG. The thickness of the metal (Ni) and polyimide mixed layer was 0.53 nm in terms of Si, and the peel strength retention (heat-resistant peel strength / normal peel strength) at this time was a good result of 55%.
The results of the measurement are shown in Table 1.
(実施例2)
ポリイミド樹脂フィルムとして、デュポン社:カプトン150ENを用いた。このポリイミド樹脂フィルムにプラズマ処理を行い、スパッタリングによりニッケルクロム合金からなるバリアー層を25.0nmの厚みに形成した。
次に、スパッタリングによりシード銅層を形成した。続いて、電気めっきにて8μmの銅導体層を形成し、ピール強度測定を行った。この結果、常態ピール強度0.80kN/m、耐熱ピール強度0.48kN/mのピール特性を持つサンプルを得た。
このように形成された金属被覆ポリイミド樹脂基板について、常態ピールにおける金属層側剥離面のポリイミドとシード層金属との混在層の厚さを飛行時間型二次イオン質量分析装置(TOF−SIMS)の深さ方向分析を用い測定を行った。
この結果、図2に示すように、バリアー金属(Ni)とポリイミド混在層の厚みがSi換算で0.41nmであり、このときのピール強度保持率(耐熱ピール強度/常態ピール強度)は55%と良好な結果であった。
上記測定の結果を、表1に示す。(Example 2)
As a polyimide resin film, DuPont: Kapton 150EN was used. This polyimide resin film was subjected to plasma treatment, and a barrier layer made of a nickel chromium alloy was formed to a thickness of 25.0 nm by sputtering.
Next, a seed copper layer was formed by sputtering. Subsequently, an 8 μm copper conductor layer was formed by electroplating, and the peel strength was measured. As a result, a sample having peel properties with a normal peel strength of 0.80 kN / m and a heat-resistant peel strength of 0.48 kN / m was obtained.
For the metal-coated polyimide resin substrate formed in this way, the thickness of the mixed layer of the polyimide and the seed layer metal on the metal layer-side release surface in the normal peel is measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Measurements were made using depth direction analysis.
As a result, as shown in FIG. 2, the thickness of the barrier metal (Ni) and polyimide mixed layer is 0.41 nm in terms of Si, and the peel strength retention (heat-resistant peel strength / normal peel strength) at this time is 55%. And good results.
The results of the measurement are shown in Table 1.
(比較例1)
ポリイミド樹脂フィルムとして、デュポン社:カプトン150ENを用いた。このポリイミド樹脂フィルムにプラズマ処理を行い、スパッタリングによりニッケルクロム合金からなるバリアー層を25.0nmの厚みに形成した。
次に、スパッタリングによりシード銅層を形成した。続いて、電気めっきにて8μmの銅導体層を形成し、ピール強度測定を行った。この結果、常態ピール強度0.79kN/m、耐熱ピール強度0.38kN/mのピール特性を持つサンプルを得た。
このように形成された金属被覆ポリイミド樹脂基板について、常態ピールにおける金属層側剥離面のポリイミドとシード層金属との混在層の厚さを飛行時間型二次イオン質量分析装置(TOF−SIMS)の深さ方向分析を用い測定を行った。
この結果、図2に示すように、バリアー金属(Ni)とポリイミド混在層の厚みがSi換算で0.77nmであり、このときのピール強度保持率(耐熱ピール強度/常態ピール強度)は48%と悪かった。
上記測定の結果を、表1に示す。(Comparative Example 1)
As a polyimide resin film, DuPont: Kapton 150EN was used. This polyimide resin film was subjected to plasma treatment, and a barrier layer made of a nickel chromium alloy was formed to a thickness of 25.0 nm by sputtering.
Next, a seed copper layer was formed by sputtering. Subsequently, an 8 μm copper conductor layer was formed by electroplating, and the peel strength was measured. As a result, a sample having peel properties with a normal peel strength of 0.79 kN / m and a heat-resistant peel strength of 0.38 kN / m was obtained.
For the metal-coated polyimide resin substrate formed in this way, the thickness of the mixed layer of the polyimide and the seed layer metal on the metal layer-side release surface in the normal peel is measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Measurements were made using depth direction analysis.
As a result, as shown in FIG. 2, the thickness of the barrier metal (Ni) and polyimide mixed layer is 0.77 nm in terms of Si, and the peel strength retention (heat-resistant peel strength / normal peel strength) at this time is 48%. It was bad.
The results of the measurement are shown in Table 1.
(比較例2)
ポリイミド樹脂フィルムとして、デュポン社:カプトン150ENを用いた。このポリイミド樹脂フィルムにプラズマ処理を行い、スパッタリングによりニッケルクロム合金からなるバリアー層を25.0nmの厚みに形成した。
次に、スパッタリングによりシード銅層を形成した。続いて、電気めっきにて8μmの銅導体層を形成し、ピール強度測定を行った結果、常態ピール強度0.77kN/m、耐熱ピール強度0.31kN/mのピール特性を持つサンプルを得た。
このように形成された金属被覆ポリイミド樹脂基板について、常態ピールにおける金属層側剥離面のポリイミドとシード層金属との混在層の厚さを飛行時間型二次イオン質量分析装置(TOF−SIMS)の深さ方向分析を用い測定を行った。
この結果、図2に示すように、バリアー金属(Ni)とポリイミド混在層の厚みがSi換算で0.97nmであり、このときのピール強度保持率(耐熱ピール強度/常態ピール強度)は40%と悪かった。
上記測定の結果を、表1に示す。(Comparative Example 2)
As a polyimide resin film, DuPont: Kapton 150EN was used. This polyimide resin film was subjected to plasma treatment, and a barrier layer made of a nickel chromium alloy was formed to a thickness of 25.0 nm by sputtering.
Next, a seed copper layer was formed by sputtering. Subsequently, an 8 μm copper conductor layer was formed by electroplating, and the peel strength was measured. As a result, a sample having peel properties of a normal peel strength of 0.77 kN / m and a heat-resistant peel strength of 0.31 kN / m was obtained. .
For the metal-coated polyimide resin substrate formed in this way, the thickness of the mixed layer of the polyimide and the seed layer metal on the metal layer-side release surface in the normal peel is measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Measurements were made using depth direction analysis.
As a result, as shown in FIG. 2, the thickness of the barrier metal (Ni) and polyimide mixed layer is 0.97 nm in terms of Si, and the peel strength retention (heat-resistant peel strength / normal peel strength) at this time is 40%. It was bad.
The results of the measurement are shown in Table 1.
以上から、TOF−SIMSにより測定したNiとポリイミドの混在層の厚さが大きくなるに従って、ピール強度保持率(耐熱ピール強度/常態ピール強度)が低下する傾向にあり、ポリイミド残渣とバリアー金属層残渣の混在層厚みがSiスパッタ速度換算で0.70nm以下であることが、ピール強度保持率を50%以上とする必要があることが確認できた。 From the above, as the mixed layer thickness of Ni and polyimide measured by TOF-SIMS increases, the peel strength retention rate (heat-resistant peel strength / normal peel strength) tends to decrease, and polyimide residue and barrier metal layer residue It was confirmed that the thickness of the mixed layer was 0.70 nm or less in terms of Si sputtering rate, and the peel strength retention rate was required to be 50% or more.
本願発明は、ポリイミド樹脂フィルムの片面又は両面に、乾式法による表面改質を行った後、乾式法によりバリアー層を形成し、その後湿式法又は乾式法によりシード層を形成し、その表層に湿式法で導電性皮膜を形成した金属被覆ポリイミド樹脂基板であって、該金属被覆ポリイミド樹脂基板を90°ピール試験した後の導電性皮膜層側の剥離面において、飛行時間型二次イオン質量分析装置(TOF−SIMS)を用いた深さ方向分析によるポリイミド残渣とバリアー金属層残渣の混在層厚みがSiスパッタ速度換算で0.70nm以下であり、150°C、168時間エージング試験後のピール強度保持率(耐熱ピール強度/常態ピール強度)が50%以上であることを特徴とする金属被覆ポリイミド樹脂基板を提供するものであり、特にポリイミドフィルムと金属層間の積層後の初期密着力を低下させることなく、エージング後の密着力を高め、したがって、ファインパターン形成に優れた効果を有し、フレキシブルプリント基板、TAB、COF等の電子部品の実装素材として用いられる無接着剤フレキシブルラミネート材、特にピール強度保持率に優れた金属被覆ポリイミド樹脂基板として有用である。 In the present invention, after surface modification by a dry method is performed on one or both sides of a polyimide resin film, a barrier layer is formed by a dry method, and then a seed layer is formed by a wet method or a dry method, and the surface layer is wet. Time-of-flight secondary ion mass spectrometer on a peeled surface on the conductive coating layer side after a 90 ° peel test of the metal-coated polyimide resin substrate with a conductive coating formed by the method The mixed layer thickness of polyimide residue and barrier metal layer residue by depth direction analysis using (TOF-SIMS) is 0.70 nm or less in terms of Si sputtering rate, and the peel strength retention after aging test at 150 ° C. for 168 hours The metal-coated polyimide resin substrate is characterized in that the ratio (heat-resistant peel strength / normal peel strength) is 50% or more. Without lowering the initial adhesion after lamination between the polyimide film and the metal layer, the adhesion after aging is enhanced, and therefore it has an excellent effect in fine pattern formation, such as flexible printed circuit boards, TAB, COF, etc. It is useful as a non-adhesive flexible laminate material used as a component mounting material, particularly as a metal-coated polyimide resin substrate having excellent peel strength retention.
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